United join fellow International Cup debutants Middlesbrough and Sparta Prague, as well as Villarreal, in Group B of the competition, which has been expanded from 16 to 24 teams and will feature 12 clubs from England and 12 across Europe.
Aston Villa, Derby County and Reading are the other British teams taking part in the competition for the first time, while Hertha BSC, Valencia and Wolfsburg are new international clubs.
PSV Eindhoven return for a third year and the club's head of academy Art Langeler says the competition, introduced to give homegrown talent the chance to test themselves against the best young players in Europe, is of great value to his players.
"The players will become better with more international experience, because they will learn to play against other playing styles and perhaps more physical teams," he said. "This will be our third season competing in the tournament which shows the high regard we put on playing these matches."
Porto, who are paired with Leicester City, Liverpool and Wolfsburg, have reached the final and semi-final in the two editions of the International Cup so far and Porto B head coach Luis Castro says playing in the competition is a "win-win" for his club.
"There are numerous mutual advantages to competing against Premier League youth teams," Castro said. "They are able to play against different style, and we are able to take our young players to a different and challenging environment.
"Last season Porto B won the Portuguese Second League title for the first time and it's fair to say that the experience of playing in the International Cup helped us in our domestic competition. It allowed the players to develop their skills and maybe even grow up faster.
"We were quick to say yes to competing again this season which shows our commitment, and also underlines how important we feel it is."
The competition, which mirrors Premier League 2 in being a mainly Under-23 format, begins with group stages that run from August until December, with the knockout stages taking place in the new year.
Derby County, Sunderland, PSV Eindhoven, Benfica
Manchester United, Middlesbrough, Sparta Prague, Villarreal
Leicester City, Liverpool, FC Porto, Wolfsburg
Chelsea, Swansea City, Dinamo Zagreb, Feyenoord
Aston Villa, Norwich City, Celtic, Valencia
Everton, Reading, Athletic Club Bilbao, Hertha BSC